Nondiffusing color formers comprising aryl j-acids in which the aryl radical is provided with a nondiffusing group



Patented Apr. 1, 1952 NONDI FFUSING COLOR FORMERS COM- PRISING ARYLJ-ACIDS IN WHICH THE .A-RYL RADICAL- IS PROVIDED NONDIFEUSING GROUP-Vsevolod Tulagin, Phillipsburg, N. J and Robert F. "Coles, "Easton,Pa., assignors to General Aniline &Film Corporation, New York, N. Y., acorporation of Delaware No Drawing. Application-January 10, 1950, SerialNo. 137,886

4 Claims.

The present invention relates to non-diffusing color formers oftheqaryl-J-acid .typein which the non-diii'using group appears in thearyl radical joined to the nitrogen atom in the 6- position of theJ-acid,-and the use of such color formers in the preparation of cyanazine dye The dye which is produced when using this color former hasvery desirable spectral char:

acteristics. The use of the color former, however, has certaindisadvantages, notably its easily broken by dilute alkalies. The use ofsuch non-diffusing color formers, therefore, limits the composition ofthe solutions employed in the processing of films by the azine method.

- Considerable attention has been given to improving the azine method bysupplying acolor former for formation of the own image which partakes ofthe desirablecharacteristics of the aryl-J-acids and which are at thesame time more stable than the long chain urethanes of such acids. As. aresultv of thiszstudy, it has'beendiscovered that color formers meetingthese requirements can be produced by including a carboxyl group in thearomatic fradical joined to the nitrogen atom of aryl-J-acids andutilizing such carboxylic acid group for the formation of amidesdesigned to render'the compounds fast to diffusion :in silverhalideemulsions and stable to dilute alkalies.

tendency ,todiifuse from a. silverhalideemulsion when located therein.Because: of this :the color former when used must be employed in thedeveloper so that a multiplicity of color development steps isinevitable.

In an efiort to overcome this objection to such color former whileretaining the desirable dye forming characteristics thereof and whileseeking to stabilize the molecule against oxidation by photographicoxidizing agents, suchas acid or alkaline .ferri-cyanide bleachsolutions, it was suggested that the aryl-Jacids be formulated aslong'alkyl chain urethanes. It was felt thatsuch products which aredescribed in United States Patent 2,480,815 would completely avoid theobjections which manifest themselves in connection with thearyl-J-acids.

It has been found, however, that the long chain urethanes .ofaryl-J-acids and the corresponding .carbox'amides do not meet the-.pre-

radical containing a chain of at least 10 carbon requisites of the artfor the reason that the urethane and the carboxamide links are ratherThe preparation and use of such color formers accordingly constitute thepurposes and objects of our invention.

The color formers, the preparation and use of which are contemplatedherein, are represented by the following structural formula."

, in which A is a radical of aromatic character and of the benzene,naphthalene, pyridine or quinoline series, X is C'O--, --OCH2CO, -CH2CO,or --NHCH2CO, Y is an aliphatic atoms or an aromatic radical containingan aliphatic chain of at least 10 carbon atoms, M

is hydrogen or a salt forming group, such as sodium, potassium, and thelike, and R is an aliphatic hydrocarbon group having less than -1-carbon atoms.

Sodium. 6- [N -propionyl-4-3-stearoylamino-5-sulfo-o-tolylcarbamylmethyl) anilino-1-naphthol-3-'sulfonate 6.-.(N-acetyl-Euoctadecylcarbamyl-Zpyridylamino-1-. naphthol-3-sulfon1c. acid The above compoundsare prepared whileutili'z'ing-carboxy aryl J-acids as 0ne-.0f theparent materials. Forthis purpose there may be employed":

The amidation of these acids, however is not .as simple as is theamidation of the ordinary types of acids. Thus it is not possible toprepare the acid chlorides of the aforementioned aryl-J- acids andcondense these with an amine. The preparation must be efiected either(1) by. forming a phosphazo compound of the desired amineand' condensingthis phosphazo compound withthe desired aryl-J-acid, or (2) by heatingwith phosphoroustrichloride a. mixture of the desired amine and thedesired aryl-J-acid suspended in pyridine. The latter reaction proceedsquite smoothly and leads-to welldefined products and is; therefore, theoperation preferred.

Theformation .of amides by: thereaction ofa phosphazo compound and anacid is described in detail; in copcnding' application Serial No.602,154, filed, by Harry W; Grimmel et al. on June 28," 1945, andentitled Process for the Production of Organic Amides, now Patent No.2,508,860.

The long chain amidesprepared as above are. non-diffusing color formers.A such, however,- theX cannot be used for-the preparation; ofmultilayer,- colonfilm because they are very easily'oxia dized; and leadto the production of an. overall brown. stain during the normalprocessing. of such. multilayer film. It has been found necessary toconvert the amides to acylamino derivatives' which give the required.cyan dye image on color forming development, are readily-soluble in.water, compatible with photographic emulsions without the production offog or desensitization of the silver halides: involved. The formation ofthe.acylami-no' derivatives can be readily effected by treating theamides with the desired acid anhydride, i. e., acetic, propionic orbutyric,'while heating-the reaction mixture.

The 'colorformers of the present invention whendispersed in silverhalide emulsion may be converted into; cyan azine dye; images; by develfomentwith .t-hede eopcrs of; U. s. Patent No."

2,486,440, and particularly with d-p-hydroxyethylaminq-G-phenylaminometanilic acid. Such color-formers are admirably suited; for use theprocessing of multilayer film by the azine method.

The dev l p rs; employ d; in suchp ocess n contain not only the desired2,4-diamino aniline and an alkali such'as sodium carbonate, sodiumhydroxide or thelike, but preferably in addition theusual adjunctssuchas an'alkali metal. bromide, i. e., potassium bromide, and an alkalimetal sulfite, such as'sodium sulfite. The, best results accrue whenthere is present in the developer a coupling aidin-the form of aninorganic or organic base, such as pyridine, quinoline or ammoniumhydroxide.

The following will serve to further illustrate the invention; but his to'be understood .thatthe same is not restricted thereto.

PREPARATION OF CARBOXY-A-RYL-J-ACIDS EXAMPLE. 1- 6-carbo:ry-2 '-naphthylJ -a.c2'd

Into a 1-liter three-neck fiask e uipped. with an agitator-and a refluxcondenser were. placed 24 g. of d-amino-z-naphthoic acid and 225 cc.

of warm water. Ammonium hydroxide. (c onc.)

- was added dropwise until a complete solution was obtained. The sodiumsalt of J -ac id (5j9..g. and neutral ammonium sulfite ,g. at 50%;)

and sodium metabisulfite (43, g.) were added.

The mixture was refluxed for 1% hours. The sodium salt of J -acid (40g.) was added, and .the mixture was refluxedfor 2 hours. The. hotmixturewas filtered and the solid tar. obtained was.

discarded The filtrate was. acidified with con-. centrated' hydrochloricacid. and. cooled. The solid was collected by filtration andfurtherpurified by crystallization from potassium chloride solution. Thematerial obtained was a cyan color former, giving dyes of approximatelythe same shade as those obtained from phenyl. J

acid.

EXAMPLE 2 7 -carbo:cy-2 -n.aphthy l J acid The "7'-carboxy-2'-naphthylJ-acid was obtained by the same procedure as that described for the6'-carboxy-2'-naphthyl J-acid.

ExAMPLn 3 8-carbo.ry naphthoxy 2 '-naphthyl .l-aczd Into a, 1-liter3-neck flask, equipped, with a stirrer and a reflux condenser, wereplaced 22 g. of 7-amino-1-naphthoxy aceticacidand. 15 0. cc. of warmwater. The. mixture was stirredand treated with concentrated ammoniumhydroxide.

solution until a complete solution had. taken place, The sodiumsaltofJ-acid (58g) neutral ammonium sulfite solution (101) g.) and. sodiummaceous earth. The filter medium'was washed The filtrate was treatedwith 250 CCuOf 30% potassium chloride. Thewith 50 cc. of Water.

oily precipitate wascollected by centrifuging, c l-issolved in 200 cc.of boiling water and the sold ti-cn was cooled. The crystalline materialso EXAMPLE 4 7'-carboxy methozcy-2'-naphthyl J-acid The 7-carboxymethoXy-2'-naphthyl J-acid may be prepared in essentially the samemanner as described in the preceding example by substituting7-amino-l-naphthoxy acetic acid for the 8-amino1-naphthoxy acetic acid.

EXAMPLE 4-carbo:cy phenyl J-acid Into a 3- liter 3-neck flask, equippedwith a stirrer and a reflux condenser was placed a solution of 770 g.J-acid paste (54%) in 1000 cc. of water containing 95 g. of sodiumhydroxide. The mixture was heated to boiling and p-amino benzoic acid(210 g.) and sodium meta bisulfite (500 g.) were added and the mixturewas refiuxed for 5 hours. The reaction mixture was diluted with 1000 cc.of water and acidified with concentrated hydrochloric acid to a pH of1-2. The resulting suspension was filtered. The solid was washedrepeatedly with water. The material was suspended in 3 liters of hotwater and potassium acetate was added until a solution had taken place.Saturated potassium chloride solution (500 cc.) was added and thesolution was cooled. The crystalline solid which had separated wascollected by filtration and washed with potassium chloride solution. Thematerial was further purified by repeated crystallization from 10%potassium chloride solution. A good test for the purity of the materialconsists of dissolving a small portion in water and acidifying withhydrochloric acid. If the substance is pure, no precipitate will beobtained while the mixture is hot; the whole mixture will set into ajelly upon cooling.

For the preparation of non-diffusing color formers, the 4-carboxy phenylJ -acid is best converted to the pyridine salt. This may be accomplishedin the following manner:

The solid obtained above is dissolved in 2 liters of hot watercontaining pyridine (200 60.). The solution is strongly acidified withconcentrated hydrochloric acid and allowed to cool. The yellowcrystalline solid so obtained is collected by filtration, washed withwater and dried.-

EXAMPLE 6 4-carborymethylphen'yl-J-acid Into a 1-liter E-necked flask,equipped with an agitator and a reflux condenser, were placed a solutionof 10 g. of sodium hydroxide in 200 cc. of water, 66 g. of J-acid and 38g. of p-amino phenyl acetic acid. The mixture was stirred until asolution was obtained and then 100 g. ofsodi- 8 collected by filtrationand dissolved in 500 cc. of hot water. Concentrated hydrochloric acid(50 cc.) was added and the suspension so obtained was cooled to 30-40 C.The product which separated at this point was collected by filtration,washed with dilute hydrochloric acid and dried.

EXAMPLE 7 3'-carbo:cy methyl amino phenyl J-acid The 3'-earboxy methylamino phenyl J acid may be prepared by the methods given above startingwith 3-aminophenyl glycine and J -acld.

EXAMPLE 8 Z-methyl-el-carbozcy-fi-quinoline J-acid Into a 1-liter3-necked flask, equipped with an agitator and; a reflux condenser wereplaced 200 cc. of water, 4 g. of sodium hydroxide, 20 g. of2-methyl-6-amino cinchoninic acid, 39 g. of J- acid and 50 g. of sodiummeta bisulfite. The mixture was refluxed for one hour and treated withan additional 13 g. of J -acid. The mixture was further refluxed for anadditional three hours. The resulting suspension was cooled andfiltered. The solid was collected by filtration and triturated with 3 Nhydrochloric acid. The insoluble material was collected by filtrationand thoroughly washed with water. The solid was dissolved in hot dilutesodium hydroxide solution; the solution was acidified with acetic acidand cooled. The crystalline solid so obtained was dissolved in hotwater,- and the solution was strongly acidified with concentratedhydrochloric acid. The dark red solid thus obtained was collooted byfiltration, washed with water, and dried. 7

EXAMPLE 9 4-carboxy-6-pyridino J-acz'd The procedure is the same as inExample 8 excepting that the 2-methyl-fi-amino-cinchoninic acid isreplaced by an equivalent amount of .6- amino nicotinic acid.

PREPARATION OF NON-DIFFUSING ARYL J-ACIDS EXAMPLE 10 A mixture of 13 g.of 5-amino-3-stearoylamino-p-toluenesulfonic acid and 10 g. ofp-carboxyphenyl J -acid in dry C. P. pyridine (150 ml.) and dry C. P.benzene ml.) is placed in a 500 ml. triple-neck flask equipped with amechanical stirrer, dropping funnel and a reflux condenser carrying awater extractor. The mixture is heated at reflux temperature for 1 hour.The water which separates in the extractor is removed, together with atotal of 100 ml. of solvents. To the stirred refluxing solution is addeddropwise over a period of hour phosphorus trichloride in dry pyridine(50 ml.). The solution is heated at reflux temperature for 3 more hours.

The solvents are removed at reduced pressure, the residue dissolved in300' ml. of hot water, filtered, and the filtrate acidified stronglywith hydrochloric acid. The solid is collected and dissolved in 500 ml.of hot water, filtered through a celite pad and the filtrate treatedwith ml. of concentrated hydrochloric acid (or until precipitation iscomplete). The mixture is heated to coagulate the solid and the solidcollected by filtration. The solid is extracted with 500 ml. of boilingglacial acetic acid. 20 cc. of acetic anhydride are added to the extractand the mixture is refluxed for /2 hour. a The mixture is fil-'tered'hot, washed with petroleum etherkand thol-3-sulfonic acid.

.-EXAMPIE 1 1 EXAMPLE 12 The procedure is the same as in Example10excepting that the p-carboxy phenyl J -acid is replaced by 7'-carboxymethoxy-2'-naphthyl J acid, and the aceticanhydride is replaced bypropionic anhydride.

The product is '6-iN-propionyli-(3 stearoylamino sulfo otolylcarbamylmethyD- anilinol -l-naphth'ol-3-sul'fonicacid.

, -EXAMPLE 13 'Ina l-liter triple-'neckedflask equipped with amechanical stirrer; dropping funnel "and reflux condenser carrying awater extractor and-heated on a m'etal bath-is placed a mixture "ofl04-g.-o'f 3-amino44-octadecylamino-benzene sulfonic a'cid pyridine:salt and 88 g. of the pyridinesal'tof pcarboxyphenyl J -acid and 300ml. of dry pyridine and 200 ml. of dry benzene. The-mixture is heated atreflux and any water-that -col 1e'cts on the separator is'taken-ofi.After the removalz'of water .is substantially "complete, a total -of250' ml. of

solvents will be removed by the extractor. Phos-- phorus 'trichloride(13.7 g.) in dry benzene (50 m1.) is added rapidly dropwise- After theaddition is complete, the solvents are removed as rapidly as possible bydistillation. Theheating is continued until a sample when removed andtreated with about 1 ml. of glacial acetic acid and 5 ml. of aceticanhydride and boiled for one minute andthen cooled produces awell-defined crystallinegproduct. The reaction'mixture is-then treatedwith'200 mlxof glacial-acetic acid and 500 m1. of acetic anhydride andheatedfonlO minutes. The solution is-then diluted with 300 ml.additional of acetic anhydride and cooled. The solid is collected,sucked as dry as possible ontheffunnel and washed with acetic anhydrideand then acetone. The-product may be purified from crystallization from50% mixture of glacial acetic-acid and absolute alcohol. It ispresumably the pyridine salt of 6-iN-acetyl l-(2-octadecyl-acetaniido 5sulfophenylcarbamyl) anilinol-l-nap'hthol-3-sulfonic acid, .-or --.of6-p- [4-(1-octadecyl- 5 -'su1fo --2 benzimidazolyl)phenylcarbamyll-N-acetylanilino 1-naphthol-3-sulfonic acid. 5;

EXAMPLE'14 v 'In a 500 ml. triple-necked flask equipped witha'mechanical stirrer, droppingfunnel and reflux condensencarrying awater'separatorand heated on ametal bath is placed. a mixture of 52 g.of thezpyridine salt of 3-amino-4-octadecylamino benzene sulfonic acidand "36g. of m-carboxy phenyl J -acid in 150 ml. of dry pyridine and 100m1. of dry benzene. The mixture is dried in a manner similar to theabove example. A solution of phosphorus trichloride (6.9 g.) and .ben-

zene (50 ml.) is added 'dropwise with stirring at reflux. After theaddition is complete, the solvents are removed by distillation and theheating of the residue is continued for one hour. The resulting syrup istreated with acetic-acid' to-obtain a solution which is diluted withacetoneand the precipitated solvent is collected. "I-he solid isrefluxed with absolute ethanol and lithium--car= bonate and theresulting solution filtered "and cooled. Low boiling petroleumetherisaddedito precipitate .the lithium salt. The lithiumsalt is dissolvedin a mixture of glacial aceticacidaand acetic anhydride and themixturerefluxediorhour to formthe N-acetylaminoderivative. The solutionis-cooled and the precipitated'salt-istool lected by filtration.

The product is 6-[N-acetyl-3-(Z-octadecylaminosulfophenylcarbamyl)aniline] -"1'-.naphthol-"3sulfonic acid.

ExAMPLnv1-5 To a solution of 54 g. of octadecylamine'and32 g. oftriethylamine in 200-cc.'of anhydrous toluene kept at '6080 -C.. isaddedslowlya solutionofil i g. of phosphorus trichloride. in '35 vcc..of.anhydrous toluene. andthe wholeisreflu'xed 'for .twoand .onehalfhours. The precipitated triethylamine.Ihy

drochloride is removed by filtration andlthephosph'azo -solution"(the.'filtrate) so obtained i's usedl withoutfurther purification.

A mixture of 10.5 g. .of potassium v (i-l8 -(ca1boxymethoxy)-2'-naphthyl] amino-.1-n'aphthol- 3-sulfonate and250-.cc..of anhydrousxylene-istrefluxed .under .a water'separator.until..no--more water-can be detected in the reflux. The placephazosolution prepared according-to the above 00.) is added and the mixtureis kept at l25 for' 20'hours. Acetic acid (8 cc.) is add'ed and themixture is refluxed for hour. ik'soluglacial-acetic acid is addedand'themixture is refluxed for hour. Aceticanhydride (20-cc9' isadded-and the mixture is-refluxed "for hour.

The resulting suspension was evaporated at -reduced pressure.Theresiduewas thoroughlyex-- cohol. The mixture was cooled andtheayel-low, solid'product was collected by filtration. 1 This substanceis a non-diffusing cyancolor former of the-probable constitution:

6 N..-.acetyl-8-octadecylcarbamylmethoxy 2-,

naphthylamino) -l-naphthol-.-3-sulfonic acid.

It can be further freed from 'resi'dua'1. .phos+ phoruscompoun'ds byboiling withaqueoustsodi USE OF NON-DIFFUSING COLOR FORMERS -..i'INSILVER HALIDE EMULSIONS l EXAMPLE 1'7 A photographic silver bromideemulsion containing per kilo of emulsion 1.5 gram of the color former ofExample is exposed, the latent image developed in a Metol-hydroquinonedeveloper, re-exposed, and the residual silver halide developed for 10minutes in a solution of the following composition: I

Potassium carbonate grams Sodium sulfite do 60 Ethylene diamine cubiccentimeters 30 4 (r3 -hydroxyethylamino) -6- phehylaminometanilic acidgrams 3 Water cubic centimeters 1000 The developed silver images arebleached with potassium ferricyanide and fixed in an acid hardening hyposolution. There is thus obtained a cyan dyestufi' image which is stableto acids and alkali, oxidizing agents.

. EXAMPLE 18 6 -phenylamino 4 (fi-hydroxyethylamino) metanilic acidgrams 8 Potassium .carbonate do 20 Sodium sulfite do 60 Potassiumbromide a do 10 Benzylamine do 5 Water to a cubic centimeters 1000 Thefilmafterdevelopment is washed, bleached in "a ferricyanide bleach, andfixed in an acid hardening hypo. There was thus obtained a positivedyestuif image in each of the three layers+a cyan dye image in thebottom layer, a magenta dye image in the middle layer, and a brilliantyellow dye image in the top layer.

It is to be understood that any of the color formers referred to abovemay be dispersed in silver halide emulsions and employed for theproduction of azine dye images.

Various modifications of the invention will occur to operators in thisfield, and we accordingly do not intend .to be limited in the patentgranted exceptas necessitated by the appended claims.

We claim:

Ln photographic silver halide emulsion containing as acolor former fastto diffusion a compound of the following constitution:

N-A- x-Nn-ar wherein A is a radical of aromatic character se- 12 lectedfrom the class consisting of those of the benzene, naphthalene, pyridineand quinoline series, X is a carbonyl containing group selected from theclass consisting of those of the following formulae: --CO-, OCH2CO,CH2CO, and --NHCH2CO-, Y is a radical selected from the class consistingof those of aliphatic radicals containing a chain of at least 10 carbonatoms and aromatic radicals containing an aliphatic chain of at least 10carbonatoms, M is selected from the class consisting of hydrogen andsalt forming groups, and R is an aliphatic hydrocarbon group having lessthan 4 carbon atoms. 1

2. The process of producing an azine dye image which comprisesdeveloping with a 2,4-diamlnoaniline, an exposed silver halide emulsioncontaining as a color former, a compound of the following formula:

JOCHs wherein A is a radical of aromatic character selected from theclass consisting of those of the benzene, naphthalene, pyridine andquinoline se-' ries, X is a carbonyl containing group selected from theclass consisting of those of the following formulae: CO-,---OCH2CO,-CH2CO, and -NHCH2CO, Y. is a radical selected from the class consistingof those of aliphatic radicals containing a chain of at least 10 carbonatoms and aromatic radicals containing an aliphatic chain of at least 10carbon atoms, and M is selected from the class consisting of hydrogenand salt forming groups.

3. A photographic silver halide emulsion con-.v taining as a colorformer fast to difiusion a com-.. pound of the following formula: s

OCH:

4. The process of producing a cyan azine dye image which comprisesdeveloping with a 2,4- diamino aniline an exposed silver halide emulsioncontaining as a color former fast to diffusion a;

' product of the following formula:

. Number OCH:

VSEVOLOD TULAGIN. ROBERT COLES.

Name Date Wilmanns Jan. 9, 1940' Tulagin Aug. 30, 1949

1. A PHOTOGRAPHIC SILVER HALIDE EMULSION CONTAINING AS A COLOR FORMERFAST TO DIFFUSION A COMPOUND OF THE FOLLOWING CONSTITUTION: